US8816036B2 - Catalysts for reaction between an isocyanate and an alcohol - Google Patents
Catalysts for reaction between an isocyanate and an alcohol Download PDFInfo
- Publication number
- US8816036B2 US8816036B2 US13/123,972 US200913123972A US8816036B2 US 8816036 B2 US8816036 B2 US 8816036B2 US 200913123972 A US200913123972 A US 200913123972A US 8816036 B2 US8816036 B2 US 8816036B2
- Authority
- US
- United States
- Prior art keywords
- compound
- anion
- diisocyanate
- functional group
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 23
- 239000012948 isocyanate Substances 0.000 title claims abstract description 18
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 64
- 150000001450 anions Chemical class 0.000 claims abstract description 58
- 239000003446 ligand Substances 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 150000004696 coordination complex Chemical group 0.000 claims abstract description 15
- 239000004814 polyurethane Substances 0.000 claims abstract description 14
- 229920002635 polyurethane Polymers 0.000 claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000129 anionic group Chemical group 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 35
- 101000597770 Homo sapiens Tropomodulin-1 Proteins 0.000 claims description 31
- 102100035291 Tropomodulin-1 Human genes 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 21
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 16
- KEBPOWLGOOTMPK-UHFFFAOYSA-N 2,2,7-trimethyloctane-3,5-dione Chemical compound CC(C)CC(=O)CC(=O)C(C)(C)C KEBPOWLGOOTMPK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- -1 sterate Chemical compound 0.000 claims description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 claims description 8
- PZMFITAWSPYPDV-UHFFFAOYSA-N undecane-2,4-dione Chemical compound CCCCCCCC(=O)CC(C)=O PZMFITAWSPYPDV-UHFFFAOYSA-N 0.000 claims description 8
- 229940126062 Compound A Drugs 0.000 claims description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 7
- CFNHVUGPXZUTRR-UHFFFAOYSA-N n'-propylethane-1,2-diamine Chemical compound CCCNCCN CFNHVUGPXZUTRR-UHFFFAOYSA-N 0.000 claims description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 7
- GUARKOVVHJSMRW-UHFFFAOYSA-N 3-ethylpentane-2,4-dione Chemical compound CCC(C(C)=O)C(C)=O GUARKOVVHJSMRW-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920005906 polyester polyol Polymers 0.000 claims description 6
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 claims description 5
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 4
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 claims description 3
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 claims description 3
- GOKHWHDASMAJQU-UHFFFAOYSA-N 2,2-dimethylnonane-3,5-dione Chemical compound CCCCC(=O)CC(=O)C(C)(C)C GOKHWHDASMAJQU-UHFFFAOYSA-N 0.000 claims description 3
- CEGGECULKVTYMM-UHFFFAOYSA-N 2,6-dimethylheptane-3,5-dione Chemical compound CC(C)C(=O)CC(=O)C(C)C CEGGECULKVTYMM-UHFFFAOYSA-N 0.000 claims description 3
- OEKATORRSPXJHE-UHFFFAOYSA-N 2-acetylcyclohexan-1-one Chemical compound CC(=O)C1CCCCC1=O OEKATORRSPXJHE-UHFFFAOYSA-N 0.000 claims description 3
- SQYMLEVHMMDXCW-UHFFFAOYSA-N 3-(2-methylpropyl)pentane-2,4-dione Chemical compound CC(C)CC(C(C)=O)C(C)=O SQYMLEVHMMDXCW-UHFFFAOYSA-N 0.000 claims description 3
- MBXOOYPCIDHXGH-UHFFFAOYSA-N 3-butylpentane-2,4-dione Chemical compound CCCCC(C(C)=O)C(C)=O MBXOOYPCIDHXGH-UHFFFAOYSA-N 0.000 claims description 3
- GSOHKPVFCOWKPU-UHFFFAOYSA-N 3-methylpentane-2,4-dione Chemical compound CC(=O)C(C)C(C)=O GSOHKPVFCOWKPU-UHFFFAOYSA-N 0.000 claims description 3
- AQGSZYZZVTYOMQ-UHFFFAOYSA-N 3-propylpentane-2,4-dione Chemical compound CCCC(C(C)=O)C(C)=O AQGSZYZZVTYOMQ-UHFFFAOYSA-N 0.000 claims description 3
- LCLCVVVHIPPHCG-UHFFFAOYSA-N 5,5-dimethylhexane-2,4-dione Chemical compound CC(=O)CC(=O)C(C)(C)C LCLCVVVHIPPHCG-UHFFFAOYSA-N 0.000 claims description 3
- KHZGUWAFFHXZLC-UHFFFAOYSA-N 5-methylhexane-2,4-dione Chemical compound CC(C)C(=O)CC(C)=O KHZGUWAFFHXZLC-UHFFFAOYSA-N 0.000 claims description 3
- IGMOYJSFRIASIE-UHFFFAOYSA-N 6-Methylheptan-2,4-dione Chemical compound CC(C)CC(=O)CC(C)=O IGMOYJSFRIASIE-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- ILPNRWUGFSPGAA-UHFFFAOYSA-N heptane-2,4-dione Chemical compound CCCC(=O)CC(C)=O ILPNRWUGFSPGAA-UHFFFAOYSA-N 0.000 claims description 3
- DGCTVLNZTFDPDJ-UHFFFAOYSA-N heptane-3,5-dione Chemical compound CCC(=O)CC(=O)CC DGCTVLNZTFDPDJ-UHFFFAOYSA-N 0.000 claims description 3
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 claims description 3
- GJYXGIIWJFZCLN-UHFFFAOYSA-N octane-2,4-dione Chemical compound CCCCC(=O)CC(C)=O GJYXGIIWJFZCLN-UHFFFAOYSA-N 0.000 claims description 3
- PJEPOHXMGDEIMR-UHFFFAOYSA-N octane-3,5-dione Chemical compound CCCC(=O)CC(=O)CC PJEPOHXMGDEIMR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- IAKOZHOLGAGEJT-UHFFFAOYSA-N 1,1,1-trichloro-2,2-bis(p-methoxyphenyl)-Ethane Chemical group C1=CC(OC)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(OC)C=C1 IAKOZHOLGAGEJT-UHFFFAOYSA-N 0.000 claims description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims description 2
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 2
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims description 2
- UHBIKXOBLZWFKM-UHFFFAOYSA-N 8-hydroxy-2-quinolinecarboxylic acid Chemical compound C1=CC=C(O)C2=NC(C(=O)O)=CC=C21 UHBIKXOBLZWFKM-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002579 carboxylato group Chemical group [O-]C(*)=O 0.000 claims description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 2
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 claims description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 2
- 125000005609 naphthenate group Chemical group 0.000 claims description 2
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001824 selenocyanato group Chemical group *[Se]C#N 0.000 claims description 2
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- NALBLJLOBICXRH-UHFFFAOYSA-N dinitrogen monohydride Chemical compound N=[N] NALBLJLOBICXRH-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- GVIIRWAJDFKJMJ-UHFFFAOYSA-N propan-2-yl 3-oxobutanoate Chemical compound CC(C)OC(=O)CC(C)=O GVIIRWAJDFKJMJ-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 235000010356 sorbitol Nutrition 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- SZCWBURCISJFEZ-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 3-hydroxy-2,2-dimethylpropanoate Chemical compound OCC(C)(C)COC(=O)C(C)(C)CO SZCWBURCISJFEZ-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MEPJABWLTPVNAN-LHSHWCRNSA-L CC(C)C/C(=C/C(=O)C(C)(C)C)O[Zn]O/C(=C\C(=O)C(C)(C)C)CC(C)C Chemical compound CC(C)C/C(=C/C(=O)C(C)(C)C)O[Zn]O/C(=C\C(=O)C(C)(C)C)CC(C)C MEPJABWLTPVNAN-LHSHWCRNSA-L 0.000 description 1
- LWCZVUPBOVTLPU-CVBJKYQLSA-L CCCCCCCC(=O)/C=C(/C)O[Zn]O/C(C)=C\C(=O)CCCCCCC Chemical compound CCCCCCCC(=O)/C=C(/C)O[Zn]O/C(C)=C\C(=O)CCCCCCC LWCZVUPBOVTLPU-CVBJKYQLSA-L 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UDHXJZHVNHGCEC-UHFFFAOYSA-N Chlorophacinone Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)C(=O)C1C(=O)C2=CC=CC=C2C1=O UDHXJZHVNHGCEC-UHFFFAOYSA-N 0.000 description 1
- UNXHWFMMPAWVPI-QWWZWVQMSA-N D-Threitol Natural products OC[C@@H](O)[C@H](O)CO UNXHWFMMPAWVPI-QWWZWVQMSA-N 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 229960000250 adipic acid Drugs 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- SKCNNQDRNPQEFU-UHFFFAOYSA-N n'-[3-(dimethylamino)propyl]-n,n,n'-trimethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)CCCN(C)C SKCNNQDRNPQEFU-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 125000000075 primary alcohol group Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
Definitions
- the invention relates to novel catalysts for the reaction between an isocyanate and an alcohol, which is a key stage in the preparation of polyurethane polymers. It relates more specifically to the use of novel catalysts which are not based on tin.
- Polyurethanes were initially used in the manufacture of plastic compounds and foams. These polymers have since been developed in very diverse fields of application, such as elastomers, thermoplastics, thermosetting resins, expanded systems, textile fibers and coating systems (coating slips for paper, wood coatings, motor vehicle paints, adhesives, and the like).
- Polyurethanes are polymers which comprise at least one urethane group (also known as carbamate group). This group results from the reaction between an alcohol group and an isocyanate group.
- the essential objective of the present invention is thus to provide a catalyst for the reaction between an isocyanate and an alcohol which is at least as active as dibutyltin dilaurate but which is not based on tin.
- Another essential objective of the present invention is to provide a catalyst which can be used in the synthesis of polyurethanes.
- a novel process for preparing a compound A having at least one urethane functional group comprising a stage 1) which consists in reacting a compound B, having at least one isocyanate functional group, with a compound D, having at least one hydroxyl functional group, in the presence of a catalytically effective amount of at least one catalyst C, characterized in that said catalyst C is a metal complex or salt of following formula (1): [Zn(L 1 ) l1 (L 2 ) l2 (Y) x ] (1)
- neutral ligand Y is not very important and a person skilled in the art will use any type of neutral ligand suitable for the zinc, so as to observe the valency of the zinc. Mention may be made, as examples, of amines, diamines, and the like.
- said catalyst C is a metal complex or salt of following formula (1): [Zn(L 1 ) l1 (L 2 ) l2 ] (1)
- the symbol L 1 of the formula (1) described above is a ⁇ -diketonato anion derived from a ⁇ -diketone of following formula (2): R 1 COCHR 2 COR 3 (2)
- the ⁇ -dicarbonylato ligand L 1 is a ⁇ -ketoesterato anion chosen from the group consisting of the anions derived from the following compounds: the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, isopentyl, n-hexyl, n-octyl, 1-methylheptyl, n-nonyl, n-decyl and n-dodecyl esters of acetylacetic acid or those described in the patent application FR-A-1 435 882.
- Another subject matter of the present invention is a process for preparing a compound A having at least one urethane functional group, comprising a stage 1) which consists in reacting a compound B, having at least one isocyanate functional group, with a compound D, having at least one hydroxyl functional group, in the presence of a catalytically effective amount of at least one catalyst C, characterized in that said catalyst C is a metal complex or salt of following formula (1): [Zn(L 1 ) l1 (L 2 ) l2 (Y) x ] (1)
- said catalyst C is a metal complex or salt of following formula (1): [Zn(L 1 ) l1 (L 2 ) l2 ] (1)
- L 2 is an anionic ligand which can be selected from the group consisting of the anions: fluoro (F ⁇ ), chloro (Cl ⁇ ), triiodo(1 ⁇ ) (I 3 ) ⁇ , difluorochlorato(1 ⁇ ) [ClF 2 ] ⁇ , hexafluoroiodato(1 ⁇ ) [IF 6 ] ⁇ , oxochlorato(1 ⁇ )(ClO) ⁇ , dioxochlorato(1 ⁇ ) (ClO 2 ) ⁇ , trioxochlorato(1 ⁇ ) (ClO 3 ) ⁇ , tetraoxochlorato(1 ⁇ ) (ClO 4 ) ⁇ , hydroxo (OH) ⁇ ,
- L 2 is an anionic ligand selected from the group consisting of the anions: acetate, oxalate, propionate, butyrate, isobutyrate, diethylacetate, benzoate, 2-ethyl-hexanoate, sterate, methoxide, ethoxide, isopropoxide, tert-butoxide, tert-pentoxide, 8-hydroxyquinolinate, naphthenate, tropolonate and the oxo O 2 ⁇ anion.
- anionic ligand selected from the group consisting of the anions: acetate, oxalate, propionate, butyrate, isobutyrate, diethylacetate, benzoate, 2-ethyl-hexanoate, sterate, methoxide, ethoxide, isopropoxide, tert-butoxide, tert-pentoxide, 8-hydroxyquinolinate, naphthenate, tropolonate and the
- the catalyst C is a metal complex or salt chosen from the group consisting of the compounds of following formulae (3) to (9):
- the amount of the catalyst is advantageously determined so that the Zn/isocyanate functional group (Zn/NCO) molar ratio is between 1/1000 and 1/50 000, preferably between 1/5000 and 1/30 000 and more preferably still between 1/8000 and 1/20 000.
- the process according to the invention is particularly suitable for the preparation of polyurethane polymers.
- the compound A having at least one urethane functional group is a polyurethane
- the compound B having at least one isocyanate functional group is a diisocyanate
- the compound D having at least one hydroxyl functional group is a polyol.
- the process according to the invention is characterized in that stage 1) consists in reacting, in the absence of moisture and in the presence of an effective amount of the catalyst C according to the invention and as described above, at least one compound B, which is an isocyanate chosen from the group consisting of monoisocyanates, diisocyanates, polyisocyanates and their mixtures, and at least one compound D, which is an alcohol chosen from the group consisting of monoalcohols, diols, polyols and their mixtures.
- stage 1) consists in reacting, in the absence of moisture and in the presence of an effective amount of the catalyst C according to the invention and as described above, at least one compound B, which is an isocyanate chosen from the group consisting of monoisocyanates, diisocyanates, polyisocyanates and their mixtures, and at least one compound D, which is an alcohol chosen from the group consisting of monoalcohols, diols, polyols and their mixtures.
- aromatic isocyanate When an isocyanate is situated on a carbon of aliphatic nature, then it is considered that the isocyanate compound is itself of aliphatic nature. Likewise, when an isocyanate functional group is attached to the backbone via a carbon of aromatic nature, then the whole of the monomer will be denoted by the expression aromatic isocyanate.
- MDI diphenylmethane diisocyanate
- TDI toluene diisocyanate
- 2,4-toluene diisocyanate and 2,6-toluene diisocyanate examples of aromatic isocyanates, of diphenylmethane diisocyanate (MDI), in particular 4,4′-diphenylmethane diisocyanate or 2,4′-diphenylmethane diisocyanate, or toluene diisocyanate (TDI), in particular 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.
- MDI diphenylmethane diisocyanate
- TDI toluene diisocyanate
- 2,4-toluene diisocyanate and 2,6-toluene diisocyanate examples of aromatic isocyanates, of diphenylmethane diisocyanate (MDI), in particular 4,4′
- alphatic isocyanates of hexamethylene diisocyanate (HMDI), 1,3-tetramethylxylylene diisocyanate, isophorone diisocyanate and dicyclohexamethylmethane diisocyanate.
- HMDI hexamethylene diisocyanate
- 1,3-tetramethylxylylene diisocyanate 1,3-tetramethylxylylene diisocyanate
- isophorone diisocyanate dicyclohexamethylmethane diisocyanate.
- IPDI isophorone diisocyanate
- the polyester polyols are generally chosen from aliphatic and aromatic polyester polyols and the mixtures of these compounds.
- polyester polyols resulting from the condensation of aliphatic, cyclic or aromatic polyols, such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, glycerol, trimethylolpropane, 1,6-hexanediol, 1,2,6-hexanetriol, butenediol, sucrose, glucose, sorbitol, pentaerythritol, mannitol, triethanolamine, N-methyl-diethanolamine and the mixtures of these compounds, with a dicarboxylic acid, such as 1,6-hexanedioic acid, dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, 1,18-octadecanedioic acid, phthalic acid, succinic acid and the mixtures of these diacids, an unsaturated an unsaturated an unsaturated an unsaturated an
- the polyester polyols are generally obtained by the use of an excess of di- or polyfunctional alcohol in their polyesterification with dicarboxylic acids or carboxylic acid anhydrides.
- the polyether polyols are generally obtained by the anionic or cationic polyaddition of cyclic monomers, such as ethylene oxide, propylene oxide or tetrahydrofuran.
- the molar masses of the polyether polyols used in the synthesis of polyurethanes generally vary from 250 to 8000. Their functionality can range from 2 to 7, depending on the nature of the molecule used as initiator.
- the end groups of these polyether diols can be primary or secondary.
- the process according to the invention is characterized in that stage 1) is carried out in the presence of an expanding agent.
- Numerous expanding agents are well known in the art and they are used in amounts varied according to the cell size desired in the final product, which is a polyurethane foam.
- the most economic of these agents is water but use is often made, alone or mixed with water, of halogenated short-chain alkanes carrying chlorine and/or fluorine.
- the expanding agents are often used in amounts amounting to up to 50% of the weight of the polyol.
- the invention also relates to the novel compounds of the formulae (7) to (9):
- a solution of 100 mmol of 97% sodium methoxide (6.12 g) in 100 ml of isopropanol is concentrated by distillation of 20%, then 100 mmol of 95% isopropyl acetoacetate (15.93 g) are added and the solution is heated at 80° C. for 1 h to give a homogeneous orange solution.
- a solution of zinc chloride (50 mmol, 7 g) in 50 ml of isopropanol is then added at 70° C. over 1 h. Heating is maintained at between 80 and 90° C. for 3 h 30 and then the sodium chloride formed is filtered off after cooling.
- the alcoholic solution is evaporated to dryness to result in 25.3 g of a paste, which is redissolved in 200 ml of ethanol. After filtering under hot conditions and evaporating to dryness, 17.2 g of a white solid are obtained (Yd 98%).
- a formulation composed of 2,4-TDI (2,4-diisocyanato-1-methylbenzene) and of polypropylene glycol with a weight of 2000 g/mol is prepared with an OH/NCO molar ratio which is equal to 0.5.
- the catalyst is added to this formulation.
- the tests are carried out in a jacketed reactor at 60° C. under a nitrogen headspace.
- the operations are carried out with the same equivalent of metal.
- Kinetic monitoring is carried out by quantitatively determining the —N ⁇ C—O (NCO) functional groups in the usual way, according to the standard AFNOR NF T 52-132 (September 1988), sometimes denoted by dibutylamine method.
- the principle of this quantitative determination is based on the reaction of the isocyanate groups with the excess di(n-butyl)amine.
- the amine is introduced in solution in toluene (1N).
- the reaction time is 15 minutes at ambient temperature.
- the excess di(n-butyl)amine is subsequently quantitatively determined by titration with hydrochloric acid (1N). Bromocresol green is used as indicator.
- a third test (Comparative 2) is carried out without the presence of catalyst and here, in order to reach the same degree of conversion of 50%, it was necessary to wait for 6 hours of reaction.
- a formulation composed of a hexamethylene diisocyanate prepolymer with 0.522 mol of NCO/100 g is prepared. 10 g of this polymer in 25 g of xylene (in the form of a solution prepared beforehand) are introduced into a reactor, followed by 6.8 g of 2-ethylhexanol (1 mol of OH/mol of NCO).
- the reaction medium is heated and, when its temperature reaches 40° C., the following are introduced:
- the activity of the novel catalysts is compared with that of dibutyltin dilaurate.
- one equivalent of dibutyltin dilaurate corresponds to 1.58 ⁇ 10 ⁇ 5 mol of tin per 10 g of hexamethylene diisocyanate prepolymer.
- the catalysts according to the invention make it possible to obtain a good degree of conversion of the isocyanate functional groups after reacting for 10 minutes. They exhibit an activity which is greater by 22% (for [Zn(TMOD) 2 ]) to 46% (for [Zn(TMOD) 2 (N,N′-dimethylethylenediamine)]) than that of [Zn(acac) 2 ].
- the catalysts according to the invention thus represent an effective alternative to the catalysts based on tin for the reaction between an isocyanate and an alcohol.
Abstract
[Zn(L1)l1(L2)l2(Y)x] (1)
-
- in which:
- l1≧1 and l2=0 or 1; with l1+l2=2, x=1 or 2,
- the symbol L1 represents a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonyl compound or an acetylacetato anion derived from a β-ketoester,
- when l1=2, the symbols L1 are identical or different,
- the symbol L2 represents an anionic ligand which is different from L1, and
- the symbol Y represents a neutral ligand;
- where the metal complex or salt C of formula (1) is not zinc diacetylacetonate.
Description
-
- Gambiroza-Jukic et al., Kinetic analysis of bulk polymerization of diisocyanate and polyol; J. Appl. Polym. Sci., 1993, vol. 47, pp. 513-519,
- Wong et al., Catalysis in competing isocyanate reactions, competing phenyl isocyanate reaction catalyzed with N,N,N′,N″,N″-pentamethyldipropylene-triamine; J. Polym. Sci.; Part A, Polym. Chem. Ed., 1986, vol. 24, pp. 2877-2890, and
- Okada, H. et al., The kinetics of the polyurethane-forming reaction between organic diisocyanates and glycols; Makromol. Chem., 1963, vol. 66, pp. 91-101.
[Zn(L1)l1(L2)l2(Y)x] (1)
-
- in which:
- l1≧1 and l2=0 or 1; with l1+l2=2, x=0, 1 or 2,
- the symbol L1 represents a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonyl compound or an acetylacetato anion derived from a β-ketoester,
- when l1=2, the symbols L1 can be identical or different,
- the symbol L2 represents an anionic ligand which is different from L1,
- the symbol Y represents a neutral ligand, and
- with the additional condition that the metal complex or salt C of formula (1) is not the compound zinc diacetylacetonate or [Zn(acac)2].
[Zn(L1)l1(L2)l2] (1)
-
- in which:
- l1≧1 and l2=0 or 1; with l1+l2=2,
- the symbol L1 represents a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonyl compound or an acetylacetato anion derived from a β-ketoester,
- when l1=2, the symbols L1 can be identical or different,
- the symbol L2 represents an anionic ligand which is different from L1, and
- with the additional condition that the metal complex or salt C of formula (1) is not the compound zinc diacetylacetonate or [Zn(acac)2].
R1COCHR2COR3 (2)
-
- in which:
- the R1 and R3 groups, which are identical or different, each represent a substituted or unsubstituted and linear or branched C1-C30 hydrocarbon radical;
- the R2 group is a hydrogen or a hydrocarbon radical, preferably a C1-C4 alkyl; and
- the R1 and R2 groups can be connected so that the β-diketone forms a ring.
[Zn(L1)l1(L2)l2(Y)x] (1)
-
- in which:
- l1≧1 and l2=0 or 1; with l1+l2=2, x=0, 1 or 2,
- the symbol L2 represents an anionic ligand which is different from L1,
- the symbol Y represents a neutral ligand, and
- the symbol L1 is a β-diketonato anion derived from a β-diketone of formula R1COCHR2COR3 (2) and said β-diketone is chosen from the group consisting of the β-diketones: 2,4-hexanedione; 2,4-heptanedione; 3,5-heptanedione; 3-ethyl-2,4-pentanedione; 5-methyl-2,4-hexanedione; 2,4-octanedione; 3,5-octanedione; 5,5-dimethyl-2,4-hexanedione; 6-methyl-2,4-heptanedione; 2,2-dimethyl-3,5-nonanedione; 2,6-dimethyl-3,5-heptane-dione; 2-acetylcyclohexanone (Cy-acac); 2,2,6,6-tetra-methyl-3,5-heptanedione (t-Bu-acac); 2,2,7-trimethyl-3,5-octanedione; 1,1,1,5,5,5-hexafluoro-2,4-pentane-dione (F-acac); benzoylacetone; dibenzoylmethane; 3-methyl-2,4-pentanedione; 3-acetylpentane-2-one; 3-acetyl-2-hexanone; 3-acetyl-2-heptanone; 3-acetyl-5-methyl-2-hexanone; stearoylbenzoylmethane; octanoyl-benzoylmethane; 4-(t-butyl)-4′-methoxydibenzoylmethane; 4,4′-dimethoxydibenzoylmethane; 4,4′-di(tert-butyl)di-benzoylmethane and 2,4-undecanedione.
[Zn(L1)l1(L2)l2] (1)
-
- in which:
- l1≧1 and l2=0 or 1; with l1+l2=2,
- the symbol L1 is a β-diketonato anion derived from a β-diketone of formula R1COCHR2COR3 (2) and said β-diketone is chosen from the group consisting of the β-diketones: 2,4-hexanedione; 2,4-heptanedione; 3,5-heptanedione; 3-ethyl-2,4-pentanedione; 5-methyl-2,4-hexanedione; 2,4-octanedione; 3,5-octanedione; 5,5-dimethyl-2,4-hexanedione; 6-methyl-2,4-heptanedione; 2,2-dimethyl-3,5-nonanedione; 2,6-dimethyl-3,5-heptanedione; 2-acetylcyclohexanone (Cy-acac); 2,2,6,6-tetramethyl-3,5-heptanedione (t-Bu-acac); 2,2,7-trimethyl-3,5-octanedione; 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (F-acac); benzoyl-acetone; dibenzoylmethane; 3-methyl-2,4-pentanedione; 3-acetylpentane-2-one; 3-acetyl-2-hexanone; 3-acetyl-2-heptanone; 3-acetyl-5-methyl-2-hexanone; stearoylbenzoylmethane; octanoyl-benzoylmethane; 4-(t-butyl)-4′-methoxydibenzoyl-methane; 4,4′-dimethoxydibenzoylmethane; 4,4′-di(tert-butyl)dibenzoylmethane and 2,4-undecanedione.
-
- (3): [Zn(t-Bu-acac)2], with (t-Bu-acac)=the 2,2,6,6-tetramethyl-3,5-heptanedionato anion or the enolate anion of 2,2,6,6-tetramethyl-3,5-heptanedione,
- (4): [Zn(EAA)2], with EAA=the ethyl acetoacetato anion or the enolate anion of ethyl acetoacetate,
- (5): [Zn(iPr-AA)2], with iPr-AA=the isopropyl acetoacetato anion or the enolate anion of isopropyl acetoacetate,
- (6): [Zn(TMOD)2], with (TMOD)=the 2,2,7-trimethyl-3,5-octanedionato anion or the enolate anion of 2,2,7-trimethyl-3,5-octanedione,
- (7): [Zn(UDD)2], with (UDD)=the 2,4-undecane-dionato anion or the enolate anion of 2,4-undecanedione,
- (8): [Zn(TMOD)2(N,N′-dimethylethylenediamine)], with (TMOD)=the 2,2,7-trimethyl-3,5-octanedionato anion or the enolate anion of 2,2,7-trimethyl-3,5-octanedione, and
- (9): [Zn(TMOD)2(N-propylethylenediamine)], with (TMOD)=the 2,2,7-trimethyl-3,5-octanedionato anion or the enolate anion of 2,2,7-trimethyl-3,5-octanedione.
-
- any isocyanate functional group for which the point of attachment of the nitrogen is a member of an aromatic ring is regarded as “aromatic”; and
- any isocyanate functional group for which the point of attachment of the nitrogen is a carbon of sp3 hybridization is regarded as “aliphatic”.
-
- (7): [Zn(UDD)2], with (UDD)=the 2,4-undecane-dionato anion or the enolate anion of 2,4-undecanedione,
- (8): [Zn(TMOD)2(N,N′-dimethylethylenediamine)], with (TMOD)=the 2,2,7-trimethyl-3,5-octanedionato anion or the enolate anion of 2,2,7-trimethyl-3,5-octanedione, and
- (9): [Zn(TMOD)2(N-propylethylenediamine)], with (TMOD)=the 2,2,7-trimethyl-3,5-octanedionato anion or the enolate anion of 2,2,7-trimethyl-3,5-octanedione.
-
- Catalyst (5): [Zn(isopropyl acetoacetato)2] or [Zn(iPr-AA)2], with iPr-AA=the isopropyl acetoacetato anion or the enolate anion of isopropyl acetoacetate
-
- Zn calc.: 18.59 weight %. found (ICP): 18.57 weight %
- IR (nm): 2989, 1617, 1514, 1246, 1170.
- Catalyst (6): [Zn(TMOD)2], with (TMOD)=the 2,2,7-trimethyl-3,5-octanedionato anion or the enolate anion of 2,2,7-trimethyl-3,5-octanedione
0.21 mol of 95% 2,2,7-trimethyl-3,5-octanedione is added at 20° C. over 1 h to a solution of 0.21 mol of potassium hydroxide in 88 g of ethanol. A solution of 0.105 mol of anhydrous zinc chloride in 16 g of ethanol is subsequently added to the homogeneous solution over 1 h. The mixture is stirred at 30° C. for 3 h, 23 g of heptane are then added and the suspension is cooled to 6° C. and then filtered. The solid is rinsed with 100 g of heptane and the filtrate is evaporated up to 90° C. under 4 mbar to give 46 g of zinc bis(2,2,7-trimethyl-3,5-octanedionate) in the form of a thick honey. - Zn calc.: 15.14 weight %. Zn found: 14.50 weight %
- IR (nm): 2953, 1574, 1509, 1410, 1162.
-
- Catalyst (7): [Zn(UDD)2], with (UDD)=the 2,4-undecanedionato anion or the enolate anion of 2,4-undecanedione
30 mmol of 2,4-undecanedione are added to a solution of 30 mmol of sodium methoxide in 10 g of ethanol at 70° C. followed, after 1 h, by a solution of 15 mmol of anhydrous zinc chloride in 2.5 g of ethanol. The mixture is stirred at 70° C. for 3 h, then 20 g of heptane are added and the suspension is cooled to 6° C. and then filtered. The solid is rinsed with 20 g of heptane and the filtrate is evaporated up to 90° C. under 4 mbar to give 6.2 g of zinc bis(2,4-undecanedionate) in the form of a pale yellow liquid of low viscosity. - Zn calc.: 15.14 weight %. Zn found: 15.74 weight %
- IR (nm): 2992, 1575, 1511, 1389, 1015, 774.
- Catalyst (7): [Zn(UDD)2], with (UDD)=the 2,4-undecanedionato anion or the enolate anion of 2,4-undecanedione
-
- [Zn(TMOD)2(N,N′-dimethylethylenediamine)] (8) prepared in the following way:
- 1 molar equivalent of N,N′-dimethylethylenediamine (example 10 mmol=0.9 g) is added over 5 min to a solution of 1 molar equivalent of Zn(TMOD)2 (example 10 mmol=4.4 g) in diisopropyl ether (example 30 ml). After 30 min, the clear solution is evaporated to give a viscous oil corresponding to the expected complex (example 10 mmol ˜5.2 g, 100%).
-
- [Zn(TMOD)2(N-propylethylenediamine)] (9), prepared in the following way:
- 1 molar equivalent of N-propylethylenediamine (example 10 mmol=1.02 g) is added over 5 min to a solution of molar equivalent of Zn(TMOD)2 (example 10 mmol=4.4 g) in diisopropyl ether (example 30 ml). After 30 min, the cloudy solution is evaporated to give a white solid corresponding to the expected complex (example 10 mmol−5.4 g, 100%).
-
- Catalyst (3): [Zn(t-Bu-acac)2], with (t-Bu-acac)=the 2,2,6,6-tetramethyl-3,5-heptanedionato anion or the enolate anion of 2,2,6,6-tetramethyl-3,5-heptanedione, CAS 14363-14-5, supplied by Sigma-Aldrich, MW=431.9 g/mol, as a 30% solution in ethyl acetate or butyl acetate after heating.
2-Operating Conditions
- Catalyst (3): [Zn(t-Bu-acac)2], with (t-Bu-acac)=the 2,2,6,6-tetramethyl-3,5-heptanedionato anion or the enolate anion of 2,2,6,6-tetramethyl-3,5-heptanedione, CAS 14363-14-5, supplied by Sigma-Aldrich, MW=431.9 g/mol, as a 30% solution in ethyl acetate or butyl acetate after heating.
-
- either 5 g of xylene, for the uncatalyzed reaction,
- or 5 g of a solution of the chosen catalyst in xylene,
which corresponds to t=0 of the reaction (starting of the stopwatch).
-
- [Zn(TMOD)2], with (TMOD)=the 2,2,7-trimethyl-3,5-octanedionato anion or the enolate anion of 2,2,7-trimethyl-3,5-octanedione (6),
- [Zn(UDD)2], with (UDD)=the 2,4-undecanedionato anion or the enolate anion of 2,4-undecanedione (7),
as well as 2 complexes of Zn(TMOD)2 with an ethylene-diamine derivative: - [Zn(TMOD)2(N,N′-dimethylethylenediamine)] (8),
- [Zn(TMOD)2(N-propylethylenediamine)] (9).
-
- dibutyltin dilaurate (DBTDL),
- dioctyltin dilaurate (DOTDL), and
- [Zn(acac)2] or zinc diacetylacetonate.
TABLE 1 | |||
DC of the | |||
N═C═O | |||
functional | |||
Molar | groups (%) | ||
Test | Catalyst | equivalent | at t = 10 min |
Comparative 1 | DBTDL | 1 | 99.2 |
Comparative 2 | DOTDL | 1 | 98.9 |
Comparative 3 | [Zn(acac)2] | 3 | 62.2 |
Invention 4 | [Zn(TMOD)2] (6) | 3 | 76.0 |
Invention 5 | [Zn(UDD)2)] (7) | 3 | 81.1 |
Invention 6 | [Zn(TMOD)2(N,N′- | 3 | 91.0 |
dimethylethylene- | |||
diamine)] (8) | |||
Invention 7 | [Zn(TMOD)2(N- | 3 | 88.8 |
propylethylene- | |||
diamine)] (9) | |||
Claims (16)
[Zn(L1)l1(L2)l2(Y)x] (1)
R1COCHR2COR3 (2)
[Zn(L1)l1(L2)l2(Y)x] (1)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0805637 | 2008-10-13 | ||
FR0805637 | 2008-10-13 | ||
PCT/EP2009/007310 WO2010043354A1 (en) | 2008-10-13 | 2009-10-12 | Novel catalysts for the reaction between an isocyanate and an alcohol |
Publications (2)
Publication Number | Publication Date |
---|---|
US20110257286A1 US20110257286A1 (en) | 2011-10-20 |
US8816036B2 true US8816036B2 (en) | 2014-08-26 |
Family
ID=40677648
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/123,972 Expired - Fee Related US8816036B2 (en) | 2008-10-13 | 2009-10-12 | Catalysts for reaction between an isocyanate and an alcohol |
Country Status (7)
Country | Link |
---|---|
US (1) | US8816036B2 (en) |
EP (1) | EP2382044B1 (en) |
JP (1) | JP5442020B2 (en) |
KR (1) | KR101400611B1 (en) |
CN (1) | CN102223953B (en) |
MX (1) | MX2011003926A (en) |
WO (1) | WO2010043354A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11312812B2 (en) * | 2016-10-12 | 2022-04-26 | Covestro Deutschland Ag | Process for producing elastomers |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012006263A1 (en) * | 2010-07-08 | 2012-01-12 | Dow Global Technologies Llc | Polyurethanes made using copper catalysts |
EP2604618A1 (en) * | 2011-12-12 | 2013-06-19 | Sika Technology AG | Metal complexes as catalysts for polyurethane compositions |
EP2604613A1 (en) * | 2011-12-12 | 2013-06-19 | Sika Technology AG | Zinc(II) complexes as catalysts for polyurethane compositions |
CN104981523B (en) * | 2012-12-20 | 2018-10-09 | 埃肯有机硅法国简易股份公司 | The organopolysiloxane composition and organopolysiloxane polycondensation catalysts of elastomer-forming can be vulcanized at ambient temperature |
JP6134006B2 (en) * | 2012-12-20 | 2017-05-24 | ブルースター・シリコーンズ・フランス・エスアエス | Articles with antifouling properties intended for underwater applications, especially marine applications |
EP2813529A1 (en) * | 2013-06-11 | 2014-12-17 | Sika Technology AG | Curable composition on the basis of polymers containing silane groups and a zinc catalyst |
CN106986976A (en) * | 2016-01-20 | 2017-07-28 | 新纶科技(常州)有限公司 | A kind of carbon monoxide-olefin polymeric |
CN110735325B (en) * | 2019-10-28 | 2021-11-16 | 科凯精细化工(上海)有限公司 | Modified epoxy group POSS fluorine-free waterproof finishing agent and preparation method thereof |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3631146A (en) * | 1966-06-22 | 1971-12-28 | Ici Ltd | Polymeric materials |
US3917722A (en) * | 1973-04-11 | 1975-11-04 | Continental Oil Co | Process for condensation of alcohols |
US20040192875A1 (en) * | 2003-03-18 | 2004-09-30 | Tosoh Corporation | Catalyst composition for production of a polyurethane resin, and method for producing a polyurethane resin |
US20060052527A1 (en) * | 2004-09-09 | 2006-03-09 | Jan Weikard | Radiation-curing binders and a process for their preparation |
US20060293486A1 (en) * | 2005-06-22 | 2006-12-28 | Eva Emmrich | Polyurethane elastomers, a process for the preparation thereof and the use thereof |
US20070178235A1 (en) * | 2004-06-14 | 2007-08-02 | Adeka Corporation | Thin film-forming material and method for producing thin film |
US20080015274A1 (en) * | 2006-07-13 | 2008-01-17 | Juan Jesus Burdeniuc | Stabilized carbanions as trimerization catalysts |
US20080207938A1 (en) * | 2007-02-26 | 2008-08-28 | Wacker Chemie Ag | Process for preparing organosilicon compounds having organyloxy groups |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4879032A (en) * | 1984-06-04 | 1989-11-07 | Allied Resin Corporation | Fluid separatory devices having improved potting and adhesive compositions |
JP3344820B2 (en) * | 1994-04-27 | 2002-11-18 | 三井化学株式会社 | Manufacturing method of flexible polyurethane foam |
EP1988109B1 (en) * | 2006-02-21 | 2013-05-29 | Mitsui Chemicals, Inc. | Polymerizable composition for polythiourethane optical material |
EP2222626A1 (en) * | 2007-12-20 | 2010-09-01 | Bluestar Silicones France | Room-temperature vulcanisable organopolysiloxane compound to give an elastomer and novel organopolysiloxane polycondensation catalysts |
FR2925511A1 (en) * | 2007-12-20 | 2009-06-26 | Bluestar Silicones France Soc | ORGANOPOLYSILOXANIC COMPOSITION VULCANIZABLE AT ROOM TEMPERATURE IN ELASTOMER AND NEW POLYCONDENSATION CATALYSTS OF ORGANOPOLYSILOXANES. |
CN102056995B (en) * | 2008-04-30 | 2013-07-10 | 蓝星有机硅法国公司 | Article having antifouling properties and intended to be used in aquatic applications, particularly marine applications |
-
2009
- 2009-10-12 MX MX2011003926A patent/MX2011003926A/en active IP Right Grant
- 2009-10-12 KR KR1020117008444A patent/KR101400611B1/en active IP Right Grant
- 2009-10-12 US US13/123,972 patent/US8816036B2/en not_active Expired - Fee Related
- 2009-10-12 EP EP09736848.4A patent/EP2382044B1/en not_active Not-in-force
- 2009-10-12 CN CN200980146920.1A patent/CN102223953B/en not_active Expired - Fee Related
- 2009-10-12 WO PCT/EP2009/007310 patent/WO2010043354A1/en active Application Filing
- 2009-10-12 JP JP2011531388A patent/JP5442020B2/en not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3631146A (en) * | 1966-06-22 | 1971-12-28 | Ici Ltd | Polymeric materials |
US3917722A (en) * | 1973-04-11 | 1975-11-04 | Continental Oil Co | Process for condensation of alcohols |
US20040192875A1 (en) * | 2003-03-18 | 2004-09-30 | Tosoh Corporation | Catalyst composition for production of a polyurethane resin, and method for producing a polyurethane resin |
US20070178235A1 (en) * | 2004-06-14 | 2007-08-02 | Adeka Corporation | Thin film-forming material and method for producing thin film |
US20060052527A1 (en) * | 2004-09-09 | 2006-03-09 | Jan Weikard | Radiation-curing binders and a process for their preparation |
US20060293486A1 (en) * | 2005-06-22 | 2006-12-28 | Eva Emmrich | Polyurethane elastomers, a process for the preparation thereof and the use thereof |
US20080015274A1 (en) * | 2006-07-13 | 2008-01-17 | Juan Jesus Burdeniuc | Stabilized carbanions as trimerization catalysts |
US20080207938A1 (en) * | 2007-02-26 | 2008-08-28 | Wacker Chemie Ag | Process for preparing organosilicon compounds having organyloxy groups |
Non-Patent Citations (2)
Title |
---|
Babcock et al., "Development and Implementation of New Volatile Cd and Zn Precursors for the Growth of Transparent Conducting Oxide Thin Films Via MOCVD," Mat. Res. Soc. Symp. Proc., 2000, pp. 317-328, vol. 623. |
Blank et al., "Catalysis of the Isocyanate-Hydroxyl Reaction by Non-Tin Catalysts," Progress in Organic Coatings, 1999, pp. 19-29, vol. 35. |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11312812B2 (en) * | 2016-10-12 | 2022-04-26 | Covestro Deutschland Ag | Process for producing elastomers |
Also Published As
Publication number | Publication date |
---|---|
KR20110093761A (en) | 2011-08-18 |
EP2382044A1 (en) | 2011-11-02 |
KR101400611B1 (en) | 2014-05-27 |
MX2011003926A (en) | 2011-11-18 |
EP2382044B1 (en) | 2018-08-01 |
US20110257286A1 (en) | 2011-10-20 |
CN102223953A (en) | 2011-10-19 |
JP2012511056A (en) | 2012-05-17 |
CN102223953B (en) | 2015-05-20 |
WO2010043354A1 (en) | 2010-04-22 |
JP5442020B2 (en) | 2014-03-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8816036B2 (en) | Catalysts for reaction between an isocyanate and an alcohol | |
Blank et al. | Catalysis of the isocyanate-hydroxyl reaction by non-tin catalysts | |
JP5548191B2 (en) | Novel catalysts and their use in the production of polyurethanes | |
US5846897A (en) | Zirconium urethane catalysts | |
CN100404577C (en) | Preparation of isocyanurate group containing polyisocyanate mixtures | |
EP1899061B1 (en) | Novel zirconium compound, catalyst and its use for polyurethane manufacture | |
WO2005058996A1 (en) | Catalyst and method of making polyurethane materials | |
CN1315904C (en) | Use of ytterbium (III) acetylacetonate as catalyst for the production of aliphatic oligocarbonate polyols | |
US9102780B2 (en) | Catalysts for reaction between an isocyanate and an alcohol | |
AU2007202504B2 (en) | Polymerization process | |
DE102007037641A1 (en) | Producing isocyanate prepolymers useful for producing adhesives and sealants comprises reacting diisocyanates with a compound with at least two isocyanate-reactive groups using dibutyltin dineodecanoate as catalyst | |
JP4250687B2 (en) | Polyurethane resin production catalyst and polyurethane resin production method | |
EP2698200B1 (en) | Thermo-latent catalysts, production and use of same | |
JP4935084B2 (en) | Polyurethane resin production catalyst and polyurethane resin production method | |
JP2005307164A (en) | Catalyst composition for producing polyurethane resin and method for producing the polyurethane resin | |
EP2493614A1 (en) | Catalysts and use of same | |
JP2000512540A (en) | Catalyst for the reaction of compounds capable of reacting with isocyanato groups with aliphatic diisocyanates having one isocyanato group bound to a primary carbon atom and one isocyanato group bound to a tertiary carbon atom | |
JP2004352977A (en) | Catalyst composition for producing polyurethane resin and method for producing polyurethane resin | |
JP2004300430A (en) | Catalyst composition for polyurethane resin production and production process of polyurethane resin |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: BLUESTAR SILICONES FRANCE, FRANCE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MALIVERNEY, CHRISTIAN;SAINT-JALMES, LAURENT;SIGNING DATES FROM 20110624 TO 20110627;REEL/FRAME:026569/0874 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551) Year of fee payment: 4 |
|
FEPP | Fee payment procedure |
Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
LAPS | Lapse for failure to pay maintenance fees |
Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20220826 |